WO2006077964A2

WO2006077964A2 - Polyimide resin, polyimide film, and polyimide laminate

Info

Publication number: WO2006077964A2
Application number: PCT/JP2006/300844
Authority: WO
Inventors: Tsuyoshi Bito; Shuta Kihara; Jitsuo Oishi
Original assignee: Mitsubishi Gas Chemical Co; Tsuyoshi Bito; Shuta Kihara; Jitsuo Oishi
Priority date: 2005-01-21
Filing date: 2006-01-20
Publication date: 2006-07-27
Also published as: TWI429684B; US20090068482A1; KR101252875B1; KR20070099617A; JP5470678B2; WO2006077964A3; US8293371B2; JPWO2006077964A1; TW200631991A

Abstract

Disclosed is a polyimide resin composed of a repeating unit represented by the formula (1) below, or alternatively a repeating unit represented by the formula (1) below and at least one repeating unit represented by the formula (2) below (wherein X is as defined in the description). [Chemical formula 1] [Chemical formula 2] The polyimide resin is good in thermoplasticity, solubility in solvents and heat resistance, while exhibiting low water absorption and excellent adhesiveness. This polyimide resin is useful as a material for the adhesive layer in a metal-clad laminate which includes an insulating base, a metal layer and an adhesive layer arranged between the insulating base and the metal layer.

Description

Specification

Polyimide resin, polyimide film and polyimide laminate

Technical field

[0001] The present invention relates to a polyimide resin having good heat resistance, solvent solubility, thermoplasticity and low water absorption, the polyimide resin film, and a metal-clad laminate using an adhesive comprising the polyimide resin. The metal-clad laminate is processed into a printed wiring board, a surface heating element, an electromagnetic shielding material, a flat cable, and the like.

Background art

[0002] Some metal-clad laminates are manufactured by bonding an insulating substrate and a metal layer through an adhesive or an adhesive film. For example, a metal-clad laminate having a three-layer structure in which an insulating base material such as an aromatic polyimide resin film and a metal layer are bonded via an adhesive film has been proposed (see Patent Document 1).

Conventionally, as an adhesive or an adhesive film, an adhesive and an adhesive film mainly made of an epoxy or acrylic resin have been used. However, since these resins have poor heat resistance, the heat resistance of the product after bonding is insufficient, and the subsequent processing conditions and use conditions are limited.

[0004] Therefore, an adhesive and an adhesive film having excellent heat resistance are required. For example, a method of applying a polyimide resin or a polyamic acid solution to an insulating substrate, then removing the solvent and optionally performing an imidization treatment to form a thermocompression bonding layer, polyimide resin or polyamic acid Is applied to a glass plate or the like, and then the solvent is removed and, in some cases, imidization treatment is performed to form a thermocompression-bondable film, and the adhesive layer and adhesive film thus formed A method of thermocompression bonding an object to be bonded such as a metal layer is disclosed (see Patent Documents 2 and 3). The adhesive layer forming method described above is roughly classified into a method using a polyimide resin solution and a method using a polyamic acid solution.

[0005] In the method using a polyamic acid solution, after the polyamic acid solution is applied to an insulating substrate or a glass plate, an imidization step at a high temperature exceeding 300 ° C is performed to form an adhesive layer or an adhesive film. It must be ... Heat resistance of metal-clad laminates formed by omitting the imidization process The property is remarkably low. In the method using a polyimide resin solution, it is only necessary to volatilize the solvent after coating, and an adhesive layer or adhesive film can be formed at a low temperature up to about 200 ° C. Therefore, a method using a polyimide resin solution is advantageous in producing a highly heat-resistant metal-clad laminate. Many conventional adhesive layers made of wholly aromatic polyimide resin were formed using a polyamic acid solution. In order to obtain a polyimide resin solution, it is necessary to be a solvent-soluble polyimide resin.

[0006] In metal-clad laminates, if there is a large amount of residual volatile components in the adhesive layer placed between the insulating substrate and the metal layer, the adhesive layer will be whitened during the soldering process that reaches a high temperature of 250 ° C or higher. If the adhesion between the insulating base material and the metal layer is significantly impaired due to swelling, foaming or the like, there is a problem (see Patent Document 4). The residual volatile components of the adhesive layer are imidization when forming the adhesive layer or adhesive film, strong water and solvent that have not been removed in the solvent removal process, moisture absorbed from the manufacturing environment, and aqueous solution in the etching process. For example, moisture absorbed during immersion. Of these, moisture is a particular problem. In order to solve the above problems, it is desired to reduce the water absorption rate, which is an indicator of the moisture content of the polyimide.

[0007] In addition, 1, 2, 4, 5—cyclohexanetetracarboxylic dianhydride and its reactive derivative obtained from 1, 2, 4, 5— A polyimide resin containing a cyclohexanetetracarboxylic acid skeleton has been disclosed (see Patent Document 6). In Example 1, 1,2,4,5-cyclohexanetetracarboxylic dianhydride and its reactive derivative were reacted with diaminodifluoromethane to form an amic acid, which was coated and then heated to imidize. Further, a transparent yellow polyimide resin film having a glass transition temperature of 304 ° C. formed by heat-pressing it is disclosed. Patent Document 5 discloses that a polyimide resin film having a glass transition temperature of 300 ° C or higher and being transparent and having little coloring can be obtained from a polyimide resin solution obtained using diaminodiphenyl ether! /

[0008] The polyimide resin having the 1,2,4,5-cyclohexanetetracarboxylic acid skeleton is relatively easy to obtain a high molecular weight, and it is easy to obtain a flexible film, and also has a solubility in a solvent. Is sufficiently large, which is advantageous in terms of film forming force. Moreover, it is extremely useful because it can easily form a flexible adhesive layer having sufficient thickness and durability. However, since the polyimide resin film described in Patent Document 6 is formed through a high-temperature imidization process as in the past, the film is colored, and the polyimide resin film described in Patent Documents 5 and 6 is In addition, the moisture absorption rate is high and the moisture absorption dimensional stability is inferior.

Patent Document 1: Japanese Patent Laid-Open No. 55-91895

Patent Document 2: JP-A-5-32950

Patent Document 3: Japanese Patent Laid-Open No. 5-59344

Patent Document 4: Japanese Patent Laid-Open No. 2001-329246

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-168800

Patent Document 6: U.S. Pat.No. 3,639,343

Disclosure of the invention

[0010] The object of the present invention is to solve the problems of wholly aromatic polyimide resins that have been conventionally used for adhesive layers, have good thermoplasticity, solvent solubility and heat resistance, low water absorption, and adhesion. Another object of the present invention is to provide a polyimide resin having excellent properties, a production method thereof, a film containing the polyimide resin, and a metal-clad laminate including an adhesive layer made of the polyimide resin.

[0011] As a result of intensive studies to solve the above problems, the present inventors have found that a polyimide resin composed of a specific repeating unit has good thermoplasticity, adhesiveness, solvent solubility and heat resistance, and low water absorption. I found that the rate. Furthermore, by using a compound having a specific structure or a specific functional group in combination as a diamine component or limiting the viscosity of the polyimide resin to a specific range, the adhesion to the metal layer and the insulating substrate is improved. I found out. Based on these findings, the present invention has been achieved.

That is, the present invention provides the following formula (1):

[Chemical 1]

Or a repeating unit represented by the formula (1) and the following formula (2): [Chemical 2]

(In the formula, X is a divalent aliphatic group having 2 to 39 carbon atoms, a divalent alicyclic group having 3 to 39 carbon atoms, a divalent aromatic group having 6 to 39 carbon atoms, or these. The main chain of X is O—, —SO—, —CH—, — C (CH) —, — OSi (CH) —, — C

2 2 3 2 3 2

H O- and S force group forces at least one selected linking group intervenes!

twenty four

X is a carboxyl group, a hydroxyl group, or a carboxylic group force. At least one selected functional group may be present. If it has such a functional group, the functional group concentration F is zero. Exceeding lmeqZg polyimide resin and below)

And at least one repeating unit force becomes polyimide榭脂THAT represented by the formula (1) is the repetition rate of the unit is 50 mole ^_0/0 or more of the total repeating units of the 0. 5gZdL N- main Provided is a polyimide resin having a logarithmic viscosity of 7 to 0.3 dLZg of the polyimide resin measured at 30 ° C. using a chilly-2-pyrrolidone solution.

Furthermore, the present invention provides a method for producing the polyimide resin.

[0014] The present invention also provides a method for producing a polyimide resin film comprising the steps of casting the polyimide resin solution on a support and evaporating and removing the organic solvent.

[0015] Further, the present invention is a metal-clad laminate including an insulating base material, a metal layer, and an adhesive layer disposed between the insulating base material and the metal layer, wherein the adhesive layer is the polyimide resin It provides a metal-clad laminate that is formed!

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The polyimide resin of the present invention (hereinafter appropriately referred to as polyimide A) has the following formula (1):

Or a repeating unit represented by the above formula (1) and the following formula (2):

The ratio of the repeating units represented by the formula (1) is 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more (respectively, respectively) of the total repeating units. is included) 100 mol ^_0/0. Polyimide A can be either a block copolymer or a random copolymer.

X in the above formula (2) is the following formula (3):

[Chemical 5]

Unlike 2 to 39 carbon atoms, a divalent aliphatic group having 3 to 39 carbon atoms, a divalent alicyclic group having 3 to 39 carbon atoms, a divalent aromatic group having 6 to 39 carbon atoms, or a combination thereof 2 Is a valent group. The main chain of X includes O—, -SO 1, -CH 1, -C (CH) 1, -OSi (CH) 1, CH

2 2 3 2 3 2 2 4

O, and one S—force group force. At least one selected bonding group may intervene. X may have at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and a carbo group (included in the main chain of X). Specific examples of X include divalent aliphatic groups such as polyalkylene, polyoxyalkylene, xylylene and their alkyl-substituted products, halogen-substituted products, carboxy-substituted products, and hydroxy-substituted products; cyclohexane, dicyclohexylmethane, Dimethylcyclohexane, isophorone, nor Divalent alicyclic groups derived from bornane and their alkyl-substituted, halogen-substituted, carboxy-substituted, hydroxy-substituted, etc .; and benzene, naphthalene, biphenylenole, diphenylmethane, diphenylether, diphenylsulfone , Benzophenone and their alkyl-substituted, halogen-substituted, carboxy-substituted, and hydroxy-substituted divalent aromatic groups. In order to improve the adhesive strength while maintaining the balance of various properties of the adhesive layer, X is preferably m-phenylene group or m-xylylene group.

[0018] When X has the above functional group, the functional group concentration F expressed in milliequivalents per lg of polyimide resin is greater than zero and less than lmeqZg polyimide resin, preferably more than zero 0.6 meq / g polyimide It is less than rosin. The functional group concentration F can be easily determined from the amount of raw material charged during synthesis. When the functional group concentration F is increased, the adhesiveness is improved, but the water absorption is increased. When the functional group concentration F is more than 1, it is preferably as small as possible within the above range as long as the desired adhesiveness is obtained.

[0019] Since polyimide A is used as a solution, its molecular weight is preferably expressed by viscosity, particularly logarithmic viscosity. The logarithmic viscosity of polyimide A is 7? (Measured at 30 ° C using 0.5gZdL of N-methyl-2-pyrrolidone solution) is 0.3-2dLZg. If it is less than 3dLZg, the strength of the polyimide resin itself is weak, and a metal-clad laminate having sufficient peel strength cannot be obtained. 2. If OdLZg is exceeded, the solution (varnish) becomes highly viscous, requiring significant dilution that is difficult to apply, making handling difficult. In order to improve the adhesive strength while maintaining the balance of the various properties of the adhesive layer, the logarithmic viscosity r? Is preferably 0.3 to ldLZg.

[0020] Usually, the molecular end of polyimide A is an amino group, a carboxyl group, or a carboxylic anhydride group. By reacting a compound having a carboxylic acid anhydride group or amino group at the molecular end, the functional group at the molecular end is reduced as much as possible, or an amino group, a carboxyl group or the like is intentionally added to the molecular end. Introduce functional groups and other substituents. In order to reduce the water absorption, a substituent having a small polarity (non-functional substituent) may be introduced at the molecular end. The water absorption of polyimide A measured by the method described later is preferably 2.5% or less. The minimum water absorption that can be achieved industrially is usually about 1%.

[0021] Polyimide A is 1, 2, 4, 5-cyclohexanetetracarboxylic acid, 1, 2, 4, 5-cyclohex Reactive derivative powers such as xanthatetracarboxylic dianhydride (HPMDA) and 1, 2, 4, 5-cyclohexanetetracarboxylic acid esters, at least one selected tetracarboxylic acid component (Y), diamine and its It can be obtained by reacting with at least one diamine component (Z) selected from reactive derivatives. As the tetracarboxylic acid component (Y), HP MDA is preferable. The tetracarboxylic acid component (Y) and the diamine component (Z) include isomers.

[0022] Examples of the diamine component (Z) include diamine, diisocyanate, and diaminodisilane, and diamine is preferred. The diamine component (diamin component (Z1)) for forming the repeating unit of the above formula (1) is 2,2-bis [4 (4-aminophenoxy) phenyl] propane (BAPP) and The diamine component (diamin component (Z2)) for forming the repeating unit of the above formula (2) is NH 2 -X-NH (X is the same as described above) and its reactive derivative.

twenty two

Reactive derivative.

[0023] The diamine component (Z2) may be any of an aromatic diamine, an aliphatic diamine, an alicyclic diamine, a reactive derivative of the diamine, and a mixture thereof. In the present invention, the term “aromatic diamine” refers to diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group, alicyclic group, aromatic group is part of the structure. Group groups and other substituents may be included. “Aliphatic diamine” refers to a diamine in which an amino group is directly bonded to an aliphatic group, and the structure includes an aliphatic group, an alicyclic group, an aromatic group, and other substituents. It's okay. “Aliphatic diamine” refers to a diamine in which an amino group is directly bonded to an alicyclic group, and an aliphatic group, alicyclic group, aromatic group, or other substituent is part of the structure. May be included. For example, 1,3-phenylenediamine (m-phenylenediamine, MPD) is an aromatic diamine because the amino group is directly bonded to the aromatic ring (benzene ring), and m-xylylenediamine (MXDA). ) Is an aliphatic diamine because the amino group is directly bonded to an aliphatic group (methylene group).

[0024] In general, when tetracarboxylic dianhydride is reacted with an aliphatic diamine or alicyclic diamine, the polyamic acid, which is an intermediate product, and the amino group derived from the aliphatic diamine or alicyclic diamine are strong. Since salt is formed, it is difficult to obtain a high molecular weight polyimide. Therefore, the solubility of the salt is relatively high, and it is necessary to devise such as using a solvent such as talesol. . However, when 1,2,4,5 cyclohexanetetracarboxylic dianhydride is used as the tetracarboxylic dianhydride, the polyamic acid and the amino group derived from the aliphatic diamine or alicyclic diamine are relatively free. Since it only forms a weakly bonded salt, the imido reaction proceeds relatively easily and can be easily increased in molecular weight.

[0025] Examples of the aliphatic diamine include ethylene diamine, hexamethylene diamine, polyethylene glycolenobis (3-aminopropyl) etherole, polypropylene glycolenoles (3-aminopropyl) ether, 1,3 bis (aminomethyl). ) Cyclohexane, 1,4 bis (aminomethyl) cyclohexane, p-xylylenediamine, m-xylylenediamine, and siloxane diamines.

[0026] Examples of the alicyclic diamine include 4,4'-diaminodicyclohexylmethane, isophorone diamine, norbornane diamine and the like.

[0027] Examples of the aromatic diamine include 1,4 phenylenediamine, 1,3 phenylenediamine, 2,4 toluene diamine, 4,4'-diaminodiphenyl ether, 3,4'-diamineaminophenol, 4,4'-diaminodiphenylmethane, 1,4 bis (4 aminophenoxy) benzene, 1,3 bis (4 aminophenoxy) benzene, 1,3 bis (3 aminophenoxy) benzene, α, α, monobis (4 aminophenol- 1) 1,4 diisopropylbenzene, α, α, 1bis (3aminophenol) 1,1,4 diisopropylbenzene, 4,4,1bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenol -Sulfone, bis [4- (4-aminophenoxy) phenol] sulfone, bis [4- (3-aminophenoxy) phenol] sulfone, 2,6 diaminonaphthalene, 1,5 diaminonaphthalene And the like.

[0028] Examples of the diamine having the above functional group include 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3,1 dihydroxy 1,4,4,1 di Aminobiphenyl, 2,4 diaminophenol, 4,4'-diaminobenzophenone, 3,3 'diaminobenzophenone, especially 3, 3, -dicarboxy 4,4'-diaminodiphenylmethane (ΜΒΑΑ), 3,5—Diaminobenzoic acid (DBA), 3, 3, —Dihydroxy—4, 4, 1 diaminobiphenol (HAB), 4, 4, 1 Diaminobenzophenone (4, 4, 1 DBP) are preferred .

[0029] Diamine having a functional group, MPD, or MXDA is used as the diamine component (Z2). Or by setting the logarithmic viscosity r? Of the polyimide resin measured at 30 ° C using a 0.5 g / dL N-methyl-2-pyrrolidone solution in the range of 0.3 to 2 dL / g. The adhesive strength of polyimide resin can be improved.

[0030] Polyimide A preferably contains the tetracarboxylic acid component (Y) with respect to 1 mole of the diamine component (Z) (diamin component (Z1) or diamine component (Z1) + diamine component (Z2)). Is produced by reacting from 0.66 to L 5 mol, more preferably from 0.9 to 1.1 mol, and even more preferably from 0.97 to L 03 mol. When the diamine having the functional group is used as the diamine component (Z2), the amount used is adjusted so that the functional group concentration F is not more than lmeqZg polyimide resin.

[0031] For example, by adjusting at least one of the conditions such as the use ratio of the raw material, the reaction temperature and time, the presence or absence and use amount of the terminal terminator, the catalyst amount, etc., the logarithmic viscosity within the above range is 7? Polyimide A can be manufactured. Those skilled in the art can easily adjust the conditions by carrying out a preliminary reaction or the like. For example, when the logarithmic viscosity of 7? Is adjusted by the molar ratio of the tetracarboxylic acid component (Y) and the diamine component (Z) and the reaction time, the closer the molar ratio is to 1, the longer the reaction time. The logarithmic viscosity of 7? Increases within the above range. The logarithmic viscosity r? Becomes smaller in the above range as the molar ratio is in the range from 0.66 to L5, the further away from 1, and the shorter the reaction time. In the solution polymerization method, the relationship between the viscosity of the reaction solution, the reaction time, and other reaction conditions, and the corresponding logarithmic viscosity is obtained in advance, and the end point of the reaction is determined based on this relationship. Polyimide A having a predetermined logarithmic viscosity r? Can be produced. The reaction time is preferably 2 to 12 hours, and the reaction temperature is preferably 180 to 205 ° C.

[0032] Polyimide A is usually produced as an organic solvent solution.

The organic solvent is not particularly limited. For example, N-methyl 2-pyrrolidone, N, N-dimethylacetamide, N, N jetylacetamide, N, N dimethylformamide, N, N jetylformamide, N —Methyl caprolatatam, hexamethyl phosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p chlorophenol, 2 chloro 4-hydroxytoluene, diglyme, triglyme, tetragram, dioxane, γ Butyrolatatone, dioxolane, cyclohexanone, cyclopentano 2 or more types may be used in combination. However, considering the performance of polyimide varnish composed of polyimide A and solvent, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAC), y-buta-mouth rataton (GBL) alone or in combination It is preferable to do this. The organic solvent is used in such an amount that the polyimide A concentration in the obtained organic solvent solution is preferably 1 to 50% by weight, more preferably 5 to 40% by weight. In addition, in the case of production by solution polymerization, a poor solvent such as hexane, heptane, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, etc. should be used to the extent that the polymer does not precipitate in combination with the above solvents. Can do.

[0033] Polyimide A includes (1) a solution polymerization method, (2) a method of preparing a polyamic acid solution, forming a film and imidizing it, and (3) a salt or imide oligomer such as a half ester salt of HPMDA. And (4) a method of reacting tetracarboxylic dianhydride and diisocyanate, and other conventionally known methods. Each method may be used in combination. The reaction of the tetracarboxylic acid component (Y) and the diamine component (Z) may be carried out in the presence of a conventionally known catalyst such as an acid, a tertiary amine or an anhydride.

[0034] In these methods, an organic solvent solution of polyimide A can be obtained directly.

The solution polymerization method (3) is preferred.

(1) A mixture containing diamine component (Z), an organic solvent, and, if necessary, a catalyst is stirred at 10 to 60 Orpm to obtain a homogeneous solution, which is kept at a temperature of 30 to 90 ° C, and a tetracarboxylic acid component ( Y) and if necessary add catalyst.

(2) Stir the mixture containing the tetracarboxylic acid component (Y), the organic solvent, and, if necessary, the catalyst at 10 to 600 rpm to obtain a homogeneous solution, which is maintained at a temperature of 30 to 90 ° C, and the diamine component (Z ) And, if necessary, a catalyst is added.

(3) After the method (1) or (2), the temperature is raised to 160 to 230 ° C., preferably 180 to 205 ° C. for 0.1 to 6 hours. This temperature depends on the boiling point of the organic solvent used. While collecting the components to be removed from the reaction system, the temperature is kept substantially constant for 0.5 to 24 hours, preferably 2 to 12 hours. If necessary, add more organic solvent and cool to the appropriate temperature.

[0035] Solution polymerization to produce polyimide A includes trimethylamine and triethylamine (TEA). , Tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-jetylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, The reaction may be performed in the presence of at least one catalyst selected from tertiary amine compounds such as N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, and isoquinoline. When used, the amount of the catalyst, preferably is 0.1 to 100 mole ^_0/0 of the tetracarboxylic acid component (Y) tool 10 mol ^_0/0 is more preferable.

[0036] A fluorine or polysiloxane surfactant may be added to the polyimide A organic solvent solution. This makes it easy to obtain an adhesive layer with good surface smoothness and a polyimide resin film.

[0037] For the polyimide resin film, the organic solvent solution of polyimide A is applied (cast) onto a smooth support such as a glass plate or a metal plate to which releasability is imparted, and the temperature is set to 50 to 350 ° C. It can be produced by evaporating and removing the organic solvent by heating. After evaporating the solvent at a temperature of 120 ° C or lower to form a self-supporting film, the film is peeled off from the support, the ends of the film are fixed, and the boiling point of the organic solvent used is 350 ° C. It is preferable to produce a polyimide resin film by drying. The pressure in the dry atmosphere may be any of reduced pressure, normal pressure, and increased pressure. The thickness of the polyimide resin film is preferably 1 to 100 μm, more preferably 2 to 50 μm. A polyimide resin film is produced by applying a polyamic acid solution on a smooth support instead of an organic solvent solution of polyimide A and heating to 50 ° C to 350 ° C to carry out a dehydration imidation reaction. it can.

[0038] The metal-clad laminate of the present invention includes an insulating base, a metal layer, and an adhesive layer made of polyimide A disposed therebetween.

In the metal-clad laminate, an organic solvent solution of polyimide A is applied to one or both of the insulating substrate and the metal layer, and the organic solvent is removed by evaporation at 50 to 350 ° C to form an adhesive layer. Produced by a method in which the base material and the metal layer are overlapped via an adhesive layer and then thermocompression bonded, or the above polyimide resin film is disposed between the insulating base material and the metal layer and thermocompression bonded. Can do. Also, a method of directly forming a metal thin film on one side of the polyimide resin film by sputtering, vapor deposition, electroless plating, etc., placing an insulating base on the other side, and heat-bonding, and insulating base An adhesive layer is formed on the surface, and a sputter is formed on the surface of the adhesive layer. A metal-clad laminate in which an insulating substrate and a metal layer are firmly bonded can also be produced by a method of forming a metal thin film by methods such as tulling, vapor deposition, and electroless plating.

The thickness of the adhesive layer is preferably 1 to: LOO μm, more preferably 2 to 50 μm. The glass transition temperature of polyimide A varies depending on the selected amine, usually 200-350 ° C, preferably 230-300 ° C. Polyimide A exhibits adhesion at temperatures above the glass transition temperature, so if the glass transition temperature is too high, the thermocompression bonding temperature will be too high, and if the glass transition temperature is too low, the heat resistance of the film itself will be insufficient.

[0039] The metal layer may be formed of a metal foil obtained by a method such as electrolysis or rolling, or the surface of the polyimide resin film or the surface of the adhesive layer formed on the insulating substrate as described above. You may form directly. The thickness of the metal layer is not particularly limited, but is preferably in the range of 1 to: LOO / zm. The material of the metal layer is preferably copper. Further, one surface (adhesion surface) or both surfaces of the metal foil may be subjected to a surface treatment so that the surface roughness Rz is 0.1 to 12 / ζ πι. In the case of copper foil generally called low profile, R _Z is preferably 0.1-2 μm, more preferably 0.4-2 / ζ πι, and even more preferably 1.0-2 / ζ πι. is there. In addition, the surface of metal foil that has not been subjected to surface treatment for bonding is usually treated with an antifungal agent, etc., so wipe the surface with a cloth soaked in acetone or other organic solvents. It is preferable to use it after

[0040] The insulating substrate of the present invention is not particularly limited as long as it can electrically insulate the metal layer. Insulating base materials include flexible type and rigid type, both of which can be used. The thickness of the insulating substrate is preferably 3 to 2000 / zm, which varies depending on the type. Flexible insulating base materials include polyimide resin (except polyimide A), polybenzimidazole, polybenzoxazole, polyamide (including aramid), polyetherimide, polyamideimide, polyester (including liquid crystalline polyester) , Polysulfone, Polyethersulfone, Polyetherketone, Polyetheretherketone, etc. Films are preferred Polyimide resin film, specifically, “Kapton EN”, “Kapton V”, “ Kapton H "(manufactured by Toray 'Dupont Co., Ltd.), trade names" Abical NPI "," Abical AH "(manufactured by Kanechi Co., Ltd.) and the like. The thickness is not particularly limited. 3 to 150 111 is preferable, 7.5 to 75 111 is preferable. [0041] Rigid-type insulating base materials include glass plates, ceramic plates, plastic plates and other insulating material plates with insulating coatings on metal plates, liquid crystal polymers, phenolic resins, and epoxy resins. And molded products obtained by impregnating and kneading various thermosetting resins with reinforcing agents such as glass fiber cloth, plastic fiber cloth and short glass fiber. Thickness is not particularly limited. 30 to 2000 m force.

[0042] As a method for thermocompression bonding, a method using a multistage (vacuum) press, a continuous press method using a pressure roll or the like can be appropriately employed.

The thermocompression bonding temperature is preferably 200 to 400 ° C, more preferably 250 to 350 ° C, and is selected in consideration of the glass transition temperature of the polyimide A used as described above. The pressure for thermocompression bonding is preferably 0.01 to 20 MPa, more preferably 0.1 to LOMPa. It is also preferable to perform thermocompression bonding in a reduced pressure atmosphere to remove the solvent and bubbles.

If the peel strength of the metal layer of the metal-clad laminate of the present invention measured by the method described later is 0.5 N / mm or more, it is preferably 0.8 NZmm or more, which is a practical force.

Example

[0043] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.

A method for measuring physical properties is shown below.

[0044] (1) IR spectrum

Measurement was performed using JIR-WINSPEC50 manufactured by JEOL Ltd.

[0045] (2) Logarithmic viscosity 7?

An N-methyl-2-pyrrolidone solution of 0.5 g / dL of polyimide was prepared. The liquid surface drop time between the marked lines of this solution was measured with a Cannon Fenceke viscometer in a constant temperature water bath at 30 ° C, and obtained by the following equation.

r? = ln (Solution falling time ZN—Methyl-2-pyrrolidone falling time) ZO. 5 The logarithmic viscosity approximates the intrinsic viscosity and can be easily obtained.

[0046] (3) Glass transition temperature

Obtained by the DSC method. Using the DSC-50 manufactured by Shimadzu Corporation, the intermediate glass transition temperature Tmg obtained by measuring at 40 to 350 ° C and at a heating rate of 10 ° C Zmin is the glass transition temperature. It was.

[0047] (4) Water absorption rate of polyimide

IPC-TM-650 2. Obtained according to the method described in 6. 2. 1.

50. 8 x 50. 8mm polyimide film is dried at 120 ° C for 1 hour, then weight (W) is measured.

0 measured. This film was immersed in distilled water at 23 ° C. for 24 hours, and after wiping off the water on the surface, the weight (W) was measured immediately.

1

Water absorption (%) = (w -W) ÷ W X 100

1 0 0

[0048] (5) Peel strength of metal layer

It was determined in accordance with JIS C6471 90 ° peeling copper foil peel strength measurement method (Method A using a rotating drum-type support bracket for peel strength measurement).

[0049] (6) Solder heat resistance

The following tests were conducted with reference to JIS C6471.

A 10 × 50 mm specimen was cut from the metal-clad laminate and left in a constant temperature room at 50% humidity and 23 ° C for 24 hours. Next, it floated in a solder bath (260 ° C and 280 ° C) for 20 seconds. A was assigned when no abnormal appearance such as swelling or peeling occurred, and C was assigned when an abnormal appearance occurred.

[0050] Example 1

In a 300 mL 5-neck glass round bottom flask equipped with a stainless steel half-moon stirrer, a nitrogen inlet tube, a Dean Stark fitted with a cooling tube, a thermometer, and a glass end cap, 4 Aminophenoxy) phenol] propane (BAPP, manufactured by Wakayama Seika Kogyo Co., Ltd.) 26. OOg (0.0.06334 mol), m-phenol-rangeamine (MPD, manufactured by Kanto Chemical Co., Ltd.) 0.76 g ( 0.00704 mol), γ-petit-mouth rataton (GBL, manufactured by Mitsubishi Chemical Co., Ltd.) 51.04 g as a solvent, and triethylamine (TEA, manufactured by Kanto Chemical Co., Ltd.) 0.356 g as a catalyst, under a nitrogen atmosphere, The solution was obtained by stirring at lOOrpm.

1, 2, 4, 5 Cyclohexanetetracarboxylic dianhydride (HPMDA, manufactured by Mitsubishi Gas Chemical Co., Inc.) 15. 77 g (0.007037 mol) and dimethylacetamide (DMAC, Mitsubishi Gas Chemical) (Made by Co., Ltd.) 12. 76 g of each was added in one batch, and then heated with a mantle heater, and heated for about 20 minutes to raise the temperature in the reaction system to 180 ° C. While collecting the components to be distilled off, the reaction system temperature was maintained at 180 ° C for 5 hours. After adding DMAC 96.20 g, the mixture was stirred at about 130 ° C. for about 30 minutes to obtain a uniform solution, and air-cooled to 100 ° C. in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20% by weight.

[0051] The obtained polyimide A solution was applied on a smooth glass plate coated with a very small amount of a release agent with a coater, and then heated on a hot plate at 100 ° C for 1 hour to self-supporting film. Formed. After fixing the peeled film on the glass plate to the stainless steel mold with several clips, it was left in a 200 ° C vacuum dryer for 5 hours to remove the solvent almost completely (less than 1% by weight). A film was obtained. IR ^ vector of this polyimide A film was measured, and characteristic absorption of imide ring was observed at V (C = 0) 1776, 1704 (cm. The logarithmic viscosity of this polyimide A was 1.05dLZg, glass transition temperature. Is 268 ° C and water absorption is 2.1% o

[0052] The polyimide A solution obtained above was applied onto a polyimide resin film having a thickness of 25 μm (trade name: Kapton 100EN, manufactured by Toray DuPont), and 100 ° C, 0.5 on a hot plate. After heating for a period of time, it was dried in a vacuum dryer at 200 ° C for 5 hours to form a 4 m thick adhesive layer on the insulating substrate. 18 m thick electrolytic copper foil (product name; 3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.)

) Was rough-treated on the adhesive layer surface to form a rough surface with Rz of 5. O / z m. An electrolytic copper foil was laminated on the adhesive layer through a rough surface. This was sandwiched between stainless mirror plates, placed between the hot plates of a hot press machine with a temperature of 330 ° C, held at contact pressure (OMPa) for 3 minutes, and then thermocompression bonded under conditions of 330 ° C, 5 MPa, 5 minutes. . Next, the metal-clad laminate was obtained by putting it between hot plates of a normal temperature press and cooling it under the condition of 5 MPa for 2 minutes.

The peel strength of the metal layer of the obtained metal-clad laminate was 1.09 NZmm, and the solder heat resistance was A.

[0053] Example 2

BAPP27. 280 g (0.006645 mol), m-xylylenediamine (MXDA, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 0.0914 g (in a 5-glass round bottom flask similar to that used in Example 1 0. 00067 mol;), NMP50.OOg, TEAO. 34 g were stirred at lOOrpm under a nitrogen atmosphere to obtain a solution.

To this, HPMDA15. 048g (0.0.06713mol), N-methyl 2 pyrrolidone (NMP, manufactured by Mitsubishi Chemical Corporation) 13. 63g were added in a lump, and then heated with a mantle heater. The reaction system temperature was raised to 195 ° C over about 20 minutes. While collecting the components to be distilled off, the temperature inside the reaction system was maintained at 195 ° C for 12 hours.

After adding 37 g of DMAC, the solution was stirred at about 130 ° C for about 30 minutes to obtain a uniform solution, and air-cooled to 100 ° C in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20% by weight.

[0054] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The IR ^ vector of this polyimide A film was measured, and V (C = 0) 1772, 1

Characteristic absorption of the imide ring was observed at 706 (cm ¹ ). The logarithmic viscosity of this polyimide A was 1.01 dL / g, the glass transition temperature was 262 ° C, and the water absorption was 1.9%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate is 0.887 NZmm, and the solder heat resistance is

A.

[0055] Example 3

Polyimide A solution obtained in Example 2, a polyimide resin film having a thickness of 25 μm as an insulating layer (trade name; Avical NPI, manufactured by Kanechi Co., Ltd.), and a metal layer having an Rz of 6. O / zm A metal-clad laminate was produced in the same manner as in Example 1 except that an electrolytic copper foil having a rough surface was used (product name: JTC, manufactured by Nikko Materials Co., Ltd.).

The peel strength of the metal layer of the obtained metal-clad laminate was 0.91 NZmm, and the solder heat resistance was A.

[0056] Example 4

In a 5-glass round bottom flask similar to that used in Example 1, HPMDA14.5 73 g (0.006501ΐ / ν), NMP40.OOg, and TEAO. 33 g were stirred at 100 rpm under a nitrogen atmosphere. To obtain a solution.

MXDA 4.427g (0.003250mol) was added to this and dissolved by stirring for a while. Then, BAPP13.343g (0.003250mol) and NMP8.51g were added together and heated with a mantle heater. The temperature inside the reaction system was raised to 195 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 195 ° C for 6 hours while collecting the components to be distilled off.

After adding DMAC71.49g, it stirred at 130 degreeC vicinity for about 30 minutes, it was set as the uniform solution, and it air-cooled in about 10 minutes to 100 degreeC, and obtained the polyimide A solution with a solid content concentration of 20 weight%. A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1774 and 1697 (cm ¹ ). The logarithmic viscosity of this polyimide A was 0.63 dL / g, the glass transition temperature was 232 ° C., and the water absorption was 2.2%. A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.95 N / mm, and the solder heat resistance was A.

[0057] Example 5

Except that the polyimide A solution obtained in Example 4 was used, Avical NPI was used as the insulating layer, and a rolled aluminum foil (product name: 1085 foil, manufactured by Nippon Foil Co., Ltd.) having a thickness of 90 μm was used as the metal layer. A metal-clad laminate was produced in the same manner as in 1.

The peel strength of the metal layer of the obtained metal-clad laminate was 1.08 NZmm, and the solder heat resistance was A.

[0058] Example 6

In a 5-glass round bottom flask similar to that used in Example 1, BAPP 19.266 g (0.04693 mol), MXDA 0.923 g (0.00678 mol), NMP 40.00 g, and TE AO. The solution was obtained by stirring at 100 rpm under a nitrogen atmosphere.

To this, HPMDAl l.690g (0.055215 monore) and NMP7.82g were calorie-free, then heated with a mantle heater, and the reaction system temperature was raised to 200 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 200 ° C. for 5 hours while collecting the components to be distilled off.

After adding 181 g of DMAC72, the mixture was stirred for about 30 minutes at around 130 ° C to obtain a uniform solution, and air-cooled to 100 ° C in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20 wt%.

[0059] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1772, 1704 (cm ¹ ). The logarithmic viscosity of this polyimide A was 0.52 dL / g, the glass transition temperature was 253 ° C., and the water absorption rate was 2.2%.

[0060] The polyimide A solution obtained above was applied onto Kapton 100EN, dried on a hot plate at 100 ° C for 0.5 hour, and then dried in a vacuum dryer at 200 ° C for 5 hours. Then, an adhesive layer having a thickness of 4 μm was formed on Kapton 100EN. Similarly, a 4 m thick adhesive layer is applied to the non-rough surface of 9 m thick electrolytic copper foil (product name; FO-WS, manufactured by Furukawa Circuit Foil Co., Ltd.) with a Rz of 1.0 m. Formed.

After the Kapton EN and copper foil obtained above were stacked so that the adhesive layers face each other, a metal-clad laminate was obtained in the same manner as in Example 1.

The peel strength of the metal layer of the obtained metal-clad laminate was 1.04 NZmm, and the solder heat resistance was A.

[0061] Example 7

In a 5-glass round bottom flask similar to that used in Example 1, BAPP27.430 g (0.006682 mol;), GBL50.89 g, and TEAO.34 g were stirred at 10 m under nitrogen atmosphere. To obtain a solution.

To this, HPMDA14. 979g (0.0.06682 mol;) and DMAC12.72g were added all at once, and then heated with a mantle heater, and the reaction system temperature was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 6 hours while collecting the components to be distilled off.

After adding 39.39 g of DMAC, the mixture was stirred at about 130 ° C for about 30 minutes to obtain a uniform solution, and air-cooled to 100 ° C in about 10 minutes to obtain a polyimide resin solution having a solid content concentration of 20% by weight.

A polyimide resin film was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. When the IR ^ vector of this polyimide resin film was measured, V (C = 0) 1 774, 1706 (cm) showed characteristic absorption of the imide ring. The logarithmic viscosity of this polyimide resin was 1. OOdLZg, The glass transition temperature was 263 ° C and the water absorption rate was 1.6%.

[0062] A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.62 NZmm, and the solder heat resistance was A.

[0063] Comparative Example 1

In a 5-glass round bottom flask similar to that used in Example 1, 4, 4′-diamino diphenyl ether (ODA, manufactured by Wakayama Seika Kogyo Co., Ltd.) 20. 624 g (0. 10299 mol), GBL52.45g and TEAO.52g were stirred at lOOrpm under nitrogen atmosphere to obtain a solution.

HPMDA23. 088g (0. 10299mol;) and DMAC13. After the addition, the mixture was heated with a mantle heater, and the reaction system temperature was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 5 hours while collecting the components to be distilled off.

After adding 43.43 g of DMAC, stir at about 130 ° C for about 30 minutes to make a homogeneous solution.

Air-cooled to 0 ° C. in about 10 minutes to obtain a polyimide resin solution having a solid concentration of 20% by weight.

[0064] A polyimide resin film was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. The IR ^ vector of this polyimide resin film was measured and V (C = 0) 1

The characteristic absorption of the imide ring was observed at 772, 1700 (cm 2. The logarithmic viscosity r? Of this polyimide was 1.06 dLZg. The glass transition temperature was 316 ° C and the water absorption was 5.5%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. The metal layer of the obtained metal-clad laminate could be easily peeled off by hand, and the peel strength was extremely low.

[0065] Comparative Example 2

In a 5-glass round bottom flask similar to that used in Example 1, α, α'-bis (3-aminophenol) -1,4-diisopropylbenzene (Bisalin, Mitsui Chemicals, Inc.) 19) 404 g (0.055 mol), GBL 38. 44 g, and TEAO. 28 g were stirred at lOOrpm in a nitrogen atmosphere to obtain a solution.

To this, HPMDA 12.627 g (0.05.633 mol;) and DMAC 9.61 g were added all at once, and then heated with a mantle heater, and the reaction system temperature was raised to 180 ° C. over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 12 hours while collecting the components to be distilled off.

After addition of 71.96 g of DMAC, the mixture was stirred for about 30 minutes at a temperature of about 130 ° C. to obtain a homogeneous solution, and air-cooled to about 100 ° C. for about 10 minutes to obtain a polyimide resin solution having a solid content concentration of 20% by weight.

[0066] A polyimide resin film was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. When the IR ^ vector of this polyimide resin film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1 774, 1704 (cm " ¹ ). The logarithmic viscosity r? Of this polyimide was 0. It was 52 dLZg, the glass transition temperature was 220 ° C, and the water absorption was 1.5%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.45 N / mm, and the solder heat resistance was A. Table 1 Diamine component Logarithmic viscosity Glass rolling Solder Water absorption Peel strength

BAPP copolymerization component V transition temperature heat resistance model type / ₀ * (dL / g) (° C) (%) (N / ram) Example

1 90 MPD 10 1.05 268 2.1 1.09 A

2 99 MXD A 1 1.01 262 1.9 0.87 A

3 99 MXD A 1 1.01 262 1.9 0.87 A

4 50 MXD A 50 0.63 232 2.2 0.95 A

5 50 MXD A 50 0.63 232 2.2 1.08 A

6 90 MXD A 13 0.52 253 2.2 1.04 A

7 100 1.00 263 1.6 0.62 A Comparative example

Ratio 1 0 ODA 100 1.06 316 5.5 <0.2 Ratio 2 0 Bisyaulin M 100 0.52 220 1.5 0.45 A mol% *: Ratio to HPMDA amount

[0068] Example 8

In a 5-glass round bottom flask similar to that used in Example 1, BAPP27.244 g (0.06637 mol), 3,3,1 dihydroxy-1,4,4,1 diaminobiphenyl (HAB, Wakayama) Seiyaku Kogyo Co., Ltd.) 0.145 g (0.0.0067 mol;), GBL 50. 90 g, and TEAO. 339 g were stirred at lOOrpm in a nitrogen atmosphere to obtain a solution.

[0069] After adding HPMDA15. 027g (0.0.06704mol) and DMAC 12.72g in a batch to this, it was heated with a mantle heater, and the temperature in the reaction system was raised to 180 ° C over about 20 minutes. . The temperature inside the reaction system was maintained at 180 ° C. for 5 hours while collecting the components to be distilled off.

After the addition of 96.38 g of DMAC, the mixture was stirred at about 130 ° C for about 30 minutes to obtain a uniform solution, and air-cooled to 100 ° C in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20% by weight.

A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, characteristic absorption of the imide ring was observed at V (C = 0) 1776, 1706 (cm " ¹ ). The functional group concentration F of this polyimide A was 0. 034 meq / g, logarithmic viscosity r? Was 1.10 dL / g, glass transition temperature was 264 ° C, and water absorption was 1.9%.

[0070] A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 1.05 N / mm and the solder heat resistance was A.

[0071] Example 9

Polyimide A solution obtained in Example 8, abicular NPI with a thickness of 25 / zm as an insulating layer, and an electrolytic copper foil with a thickness of 18 m having a rough surface with a Rz of 6.0 m as a metal layer (product name: JTC The metal-clad laminate was manufactured in the same manner as in Example 1 except that Nikko Materials Co., Ltd. was used. The peel strength of the metal layer of the obtained metal-clad laminate was 1. lON / mm, solder Heat resistance was only A.

[0072] Example 10

In a 5-glass round bottom flask similar to that used in Example 1, BAPP26. 956 g (0.06566 mol), 3,5-diaminobenzoic acid (DBA, manufactured by ACROS) 0.309 g (0. 0 0203 mol;), GBL 50.93 g, and TEAO. 34 g were stirred at lOOrpm under a nitrogen atmosphere to obtain a solution.

To this, HPMDA15.175 g (0.006769 mol;) and DMAC12.73 g were added all at once, and then heated with a mantle heater, and the reaction system temperature was raised to 180 ° C. over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 4 hours while collecting the components to be distilled off.

After the addition of 96.34 g of DMAC, the solution was stirred at about 130 ° C for about 30 minutes to obtain a uniform solution, and air-cooled to 100 ° C in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20% by weight.

[0073] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, characteristic absorption of the imide ring was observed at V (C = 0) 1776, 1 706 (cm. The functional group concentration F of this polyimide A was 0.051 meqZg, logarithm The viscosity r? Was 0.78 dL / g, the glass transition temperature was 261 ° C, and the water absorption was 2.0 (%).

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.89 (NZmm), and the solder heat resistance was A.

[0074] Example 11

Using the polyimide A solution obtained in Example 10, 25 / zm thick Avical NPI as the insulating layer, and 90 μm thick rolled aluminum foil (product name: 1085 foil, manufactured by Nippon Foil Co., Ltd.) as the metal layer A metal-clad laminate was obtained in the same manner as in Example 1 except that. The rolled aluminum foil was used after the adhesive surface was wiped with a cloth soaked with acetone.

The peel strength of the metal layer of the obtained metal-clad laminate was 0.97 NZmm, and the solder heat resistance was A.

[0075] Example 12

In a 5-glass round bottom flask similar to that used in Example 1, BAPP26. 773 g (0.0 06522 monole), 3, 3, monodicanoloxy 4, 4, monodiaminodimethane (MBA A, Wakayama Seimitsu) 0.577 g (0.000020 mol), GBL 50. 91 g, and TE AO. 34 g were stirred at lOOrpm in a nitrogen atmosphere to obtain a solution.

HPMDA15.072g (0.006724mol;), DMAC12.73g After the addition, the mixture was heated with a mantle heater, and the reaction system temperature was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 6 hours while collecting the components to be distilled off.

[0076] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1776 and 1 706 (cm-1).

The functional group concentration F of this polyimide A was 0.1101 meq / g, the logarithmic viscosity r? Was 1.05 dL / g, the glass transition temperature was 263 ° C., and the water absorption was 1.9%. A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.81 (NZmm), and the solder heat resistance was A.

[0077] Example 13

In a 5-glass round bottom flask similar to that used in Example 1, BAPP26.874 g (0.0.06546 monole), 4,4,1 diaminobenzophenone (4,4,1 DBP-ALDRICH) A solution was obtained by stirring 0.40 g (0.000020 mol), GBL 50.92 g, and TEAO. 34 g under nitrogen atmosphere at lOOrpm.

HPMDA15.129g (0.06749mol;) and DMAC12.73g were added all at once, and then heated with a mantle heater, and the temperature in the reaction system was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 6 hours while collecting the components to be distilled off.

After adding DMAC96.35g, it stirred for about 30 minutes at about 130 degreeC, and it was set as the homogeneous solution, and it air-cooled to about 100 degreeC in about 10 minutes, and obtained the polyimide A solution with a solid content concentration of 20 weight%.

[0078] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1776, 1704 (cm-1).

The functional group concentration F of this polyimide A was 0.051 meq / g, the logarithmic viscosity r? Was 0.74 dL / g, the glass transition temperature was 262 ° C., and the water absorption was 1.7%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.86 N / mm, and the solder heat resistance was A.

[0079] Comparative Example 3

In a 5-glass round bottom flask similar to that used in Example 1, BAPP15.436 g (0.003760 mol), HAB4.005 g (0.001852 mol), GBL38.43 g, and TEAO. The solution was obtained by stirring at lOOrpm under a nitrogen atmosphere.

HPMDA12.581g (0.05612mol;) and DMAC9.61g were added at once to this, and then heated with a mantle heater, and the temperature in the reaction system was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 6 hours while collecting the components to be distilled off.

After adding 71.97 g of DMAC, the solution was stirred for about 30 minutes at around 130 ° C. to obtain a uniform solution, and air-cooled to 100 ° C. for about 10 minutes to obtain a polyimide solution having a solid content concentration of 20% by weight.

[0080] A polyimide film was obtained in the same manner as in Example 1 except that the obtained polyimide solution was used. When the IR ^ vector of this polyimide film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1772 and 1704 (cm-1). The polyimide had a functional group concentration F of 1.235 meq / g, a logarithmic viscosity r? Of 0.89 dL / g, a glass transition temperature of 300 ° C., and a water absorption of 5.0%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide solution was used. The peel strength of the metal layer of the resulting metal-clad laminate was 1. OON / mm and the solder heat resistance was C.

[0081] [Table 2]

Table 2 Diamine Component Functional Group Concentration F Logarithmic Viscosity Force ^^ Transfer Water Absorption Peel Strength

BAPP copolymer component V

Mol ^_0/0

(meq / g) (dL / g) (N / mm) Example

8 99 HAB 1 0. 034 1. 10 264 1. 9 1. 05 A

9 99 HAB 1 0. 034 1. 10 264 1. 9 1. 10 A

1 0 97 DBA 3 0. 051 0. 78 261 2. 0 0. 89 A 1 1 97 DBA 3 0. 051 0. 78 261 2. 0 0. 97 A

1 2 97 MBAA 3 0. 101 1. 05 263 1. 9 0. 81 A 1 3 97 4, 4,-DBP 3 0. 051 0. 74 262 1. 7 0. 86 A Comparative example

3 67 HAB 1. 235 0. 89 300 5. 0 1. 00 c

[0082] Example 14

In a 5-glass round bottom flask similar to that used in Example 1, BAPP27.533 g (0.006707 mol;), GBL50.901 g, and TEAO.336 g were stirred at lOOr pm under nitrogen atmosphere. To obtain a solution.

To this, HPMDA14.885g (0.006640 monore) and DMAC 12.725g were added together, and then heated with a mantle heater, and the reaction system temperature was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C for 3 hours while collecting the components to be distilled off.

[0083] DMAC96. After adding 374 g, the mixture was stirred for about 30 minutes at a temperature of about 130 ° C to obtain a homogeneous solution, and then cooled to 100 ° C in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20 wt%. .

A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1774, 17 06 (cm ¹ ). The logarithmic viscosity of this polyimide A was 7 IdLZg, the glass transition temperature was 262 ° C., and the water absorption was 1.7%.

[0084] A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.86 N / mm, and the solder heat resistance was A.

[0085] Example 15

In a 5-glass round bottom flask similar to that used in Example 1, BAPP 14.214 g (0.003463 mol), 4, 4, monobis (4-aminophenoxy) biphenyl (BAPB, Sei Wakayama) (Manufactured by Sakai Kogyo Co., Ltd.) 12. 757 g (0.003463 mol), GBL50. 995 g, and TEAO. 350 g were stirred at lOOrpm in a nitrogen atmosphere to obtain a solution.

To this, HPMDA15.524g (0.006925 monore) and DMAC12.749g were added in a lump, and then heated with a mantle heater, and the reaction system temperature was raised to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C. for 4 hours while collecting the components to be distilled off.

After adding DMAC96.256g, it stirred for about 30 minutes at the temperature of about 130 degreeC, and it was set as the homogeneous solution, and it air-cooled in about 10 minutes to 100 degreeC, and obtained the polyimide A solution with a solid content concentration of 20 weight%.

[0086] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When IR ^ vector of this polyimide A film was measured, V (C = 0) 1779, 17 The characteristic absorption of the imide ring was observed at 04 (cm- ¹ ). This polyimide A had a logarithmic viscosity of 7? 0.95dLZg, a glass transition temperature of 278 ° C, and a water absorption of 1.9%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.81 NZmm, and the solder heat resistance was A.

[0087] Example 16

Polyimide A solution obtained in Example 15, an abical NPI with a thickness of 25 m as an insulating layer, an electrolytic copper foil with a thickness of 18 m having a rough surface with a Rz of 6.0 m as a metal layer (product name; A metal-clad laminate was produced in the same manner as in Example 1 except that JTC (Nikko Materials Co., Ltd.) was used.

The peel strength of the metal layer of the obtained metal-clad laminate was 0.85 N / mm, and the solder heat resistance was A.

[0088] Example 17

BAPP24. 158 g (0.05885 mol), p-xylylenediamine (PXDA, manufactured by Mitsubishi Gasy Chemical Co., Ltd.) in a round glass round bottom flask similar to that used in Example 1. 004 g (0. 01471 mol;), NMP50. OOOg, and TEAO. 372 g were stirred at lOOr pm under a nitrogen atmosphere to obtain a solution.

HPMDA16.490g (0.007356mol;) and NMP13.997g were added in a lump to each, and then heated with a mantle heater, and the reaction system temperature was raised to 195 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 195 ° C for 3 hours while collecting the components to be distilled off.

After adding DMAC96.023g, the mixture was stirred for about 30 minutes at a temperature of about 130 ° C to obtain a homogeneous solution, and then cooled to 100 ° C in about 10 minutes to obtain a polyimide A solution having a solid content concentration of 20% by weight.

[0089] A polyimide A film was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. When the IR ^ vector of this polyimide A film was measured, the characteristic absorption of the imide ring was observed in V (C = 0) 1772 and 16 99 (cm ¹ ). This polyimide A had a logarithmic viscosity of 7? Of 0.7 IdL / g, a glass transition temperature of 261 ° C, and a water absorption of 2.2%.

A metal-clad laminate was obtained in the same manner as in Example 1 except that the obtained polyimide A solution was used. The peel strength of the metal layer of the obtained metal-clad laminate was 0.85 N / mm, and the solder heat resistance was A.

[0090] Example 18

The polyimide A solution obtained in Example 17, an abical NPI with a thickness of 25 m as an insulating layer, and a rolled aluminum foil (product name: 1085 foil, manufactured by Nippon Foil Co., Ltd.) with a thickness of 90 μm as a metal layer. A metal-clad laminate was obtained in the same manner as in Example 1 except that it was used. The rolled aluminum foil was used after the adhesive surface was wiped with a cloth soaked with acetone.

The peel strength of the metal layer of the obtained metal-clad laminate was 0.95 N / mm, and the solder heat resistance was A.

[0091] Comparative Example 4

To this was added HPMDA23.088g (0.10299mol;) and DMAC13.llg in a lump, and then heated with a mantle heater to raise the temperature in the reaction system to 180 ° C over about 20 minutes. The temperature inside the reaction system was maintained at 180 ° C for 3 hours while collecting the components to be distilled off.

After adding 94.43 g of DMAC, the mixture was stirred for about 30 minutes at a temperature of about 130 ° C. to obtain a homogeneous solution, and air-cooled to 100 ° C. in about 10 minutes to obtain a polyimide resin solution having a solid content concentration of 20% by weight.

[0092] A polyimide resin film was obtained in the same manner as in Example 1 except that the obtained polyimide resin solution was used. When the IR ^ vector of this polyimide resin film was measured, characteristic absorption of the imide ring was observed in V (C = 0) 1 772 and 1700 (cm " ¹ ). The logarithmic viscosity r? Of this polyimide was 0. The glass transition temperature was 315 ° C and the water absorption was 5.7%.

[0093] [Table 3] 3 tables

隱 A _B m Difficulty ^ Absorption rate Peeling degree is mol% mol% Type mol% (dL / g) (° C) (%) (N / ram) i≤ Example

1 4 99 100 1 0. 71 262 1. 7 0. 86 A

1 5 100 50 BAPB 50 0. 95 278 1. 9 0. 81 A

1 6 100 50 BAPB 50 0. 95 278 1. 9 0. 85 A

1 7 100 80 PXDA 20 0. 71 261 2. 2 0. 85 A

1 8 100 80 PXDA 20 0. 71 261 2. 2 0. 95 A Comparative example

4 100 —— ODA 100 0. 90 315 5. 7 <0. 2 ——

Industrial applicability

The polyimide resin of the present invention has good thermoplasticity, solvent solubility and heat resistance, low water absorption, and excellent adhesion, so it is processed into printed wiring boards, surface heating elements, electromagnetic shielding materials, flat cables, etc. It is useful as a material for the adhesive layer of a metal-clad laminate.

Claims

The following formula (1)

[Chemical 1]

Or a repeating unit represented by the formula (1) and the following formula (2):

2 2 3 2 3 2

H O- and S force group forces at least one selected linking group intervenes!

twenty four

And at least one repeating unit force becomes polyimide榭脂THAT represented by the formula (1) is the repetition rate of the unit is 50 mole ^_0/0 or more of the total repeating units of the 0. 5gZdL N- main Polyimide resin having a logarithmic viscosity 7? Of 0.3-2dLZg of the polyimide resin measured at 30 ° C using a chilly-2 pyrrolidone solution

[2] The polyimide resin according to claim 1, wherein X in the formula (2) is an m-phenylene group or an m-xylylene group.

[3] The polyimide resin according to claim 1, wherein the logarithmic viscosity r? Is 0.3 to ldLZg.

[4] Water absorption is 2.

The polyimide resin according to any one of claims 1 to 3, which is 5% or less. [5] A polyimide resin solution containing the polyimide resin according to any one of claims 1 to 4 and an organic solvent.

[6] Reactivity of 1, 2, 4 5 cyclohexane tetracarboxylic acid, 1, 2, 4, 5 cyclohexane tetracarboxylic dianhydride and 1, 2, 4, 5 cyclohexane tetracarboxylic acid At least one tetracarboxylic acid component (Y) that is selected as a group strength that also induces physical strength and a diamine component (Z) that is a mixture of the diamine component (Z1) or the diamine component (Z1) and the diamine component (Z2) Including the step of reacting with the following formula (1):

[Chemical 3]

2 2 3 2 3 2

H O- and S force group forces at least one selected linking group intervenes!

twenty four

And a ratio of the repeating units of the formula (1) is 50 mol% or less of all repeating units,

(a) The diamine component (Z1) is 2, 2 bis [4 (4-aminophenoxy) phenyl] propaline. And its reactive derivative power group power is at least one selected compound;

(b) The diamine component (Z2) is different from the diamine component (Z1), and NH -X-NH (X

2) As in (2)) and the reactive derivative power group power of at least one selected compound;

(c) When the diamine component (Z) is a mixture, the amount of the diamine component (Z1) used is 50 mol% or more of the total amount of the diamine component (Z1) and the diamine component (Z2).

A method for producing a polyimide resin.

[7] The diamine component (Z1) is at least one compound selected from the group power of 2, 2 bis [4 (4-aminophenoxy) phenol] propane and its reactive derivative, and the diamine component ( The polyimide resin according to claim 6, wherein Z2) is m-phenylenediamine, m-xylylenediamine, and their reactive derivative power group power. Manufacturing method.

8. The method for producing a polyimide resin according to claim 6, wherein the logarithmic viscosity r? Is 0.3 to ldLZg.

9. The method for producing a polyimide resin according to any one of claims 6 to 8, wherein the reaction is carried out in an organic solvent solution with heating in the presence or absence of a catalyst to obtain a polyimide resin solution.

10. The method for producing a polyimide resin according to claim 9, wherein the catalyst is a tertiary amine.

11. The method for producing a polyimide resin according to claim 9 or 10, wherein the heating is performed at a temperature of 180 to 205 ° C for 2 to 12 hours.

[12] A polyimide resin solution comprising the steps of casting the polyimide resin solution according to claim 5 or the polyimide resin solution obtained by the production method according to claim 9 on a support and evaporating and removing the organic solvent. A method for producing a fat film.

[13] The organic solvent is evaporated and removed at a temperature of 120 ° C or lower to form a self-supporting film, the end of the film peeled off from the support is fixed, and dried at a boiling point of the organic solvent to 350 ° C. The method for producing a polyimide resin film according to claim 12.

[14] An insulating base material, a metal layer, and the polyimide resin according to any one of claims 1 to 3, or the polyimide resin obtained by the production method according to any one of claims 6 to 8. And a metal-clad laminate including an adhesive layer disposed between the insulating substrate and the metal layer.

[15] The adhesive layer is obtained by the polyimide resin solution according to claim 5 or the production method according to claim 9. 15. The metal-clad laminate according to claim 14, wherein the obtained polyimide resin solution is applied to one or both of the insulating substrate and the metal layer, and then the organic solvent is removed by evaporation.

[16] The metal-clad laminate according to claim 14, wherein the adhesive layer is formed of a polyimide resin film obtained by the production method according to claim 12.

17. The metal-clad laminate according to any one of claims 14 to 16, wherein the polyimide resin has a glass transition temperature of 300 ° C or lower.

[18] The surface roughness Rz of the surface of the metal layer facing the adhesive layer is 0.1 to 2 / z m.

The metal-clad laminate according to any one of 17 above.

[19] The metal-clad laminate according to any one of [14] to [18], wherein the peel strength of the metal layer measured by the peel strength measurement method for copper foil by 90 ° peel of JIS C6471 is 0.5 NZmm or more.